Use of phenethyl acrylamides, novel phenethyl acrylamides,...

Details Use of phenethyl acrylamides, novel phenethyl acrylamides,... Use of phenethyl acrylamides, novel phenethyl acrylamides,...

2002-12-04

2004-02-24

Kumar, Shailendra (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C564S161000, C514S617000, C514S522000, C558S414000

Reexamination Certificate

active

06696607

ABSTRACT:

The present invention relates to the use of phenethylacrylamides of the formula I
in which the substituents have the following meanings:
X is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
8
-alkoxy, C
1
-C
4
-haloalkoxy and —O—C(R
a
,R
b
)—C≡C—R
6
;
R
a
,R
b
independently of one another are hydrogen and C
1
-C
6
-alkyl;
R
c
is hydrogen, C
1
-C
8
-alkyl, C
3
-C
8
-cycloalkyl and phenyl which can be substituted by halogen, cyano, nitro, CF
3
, C
1
-C
4
-alkyl and/or C
1
-C
4
-alkoxy;
m,n independently of one another are 1 to 4, it being possible for the radicals X and Y to be different if m or n is greater than 1;
Y is halogen, nitro, cyano, C
1
-C
4
-alkyl, CF
3
, C
1
-C
4
-alkoxy and phenyl;
R
1
, R
2
independently of one another are hydrogen, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy and CF
3
;
R
3
,R
4
,R
5
,R
6
independently of one another are hydrogen, C
1
-C
4
-alkyl and C
1
-C
4
-alkoxy or
R
3
and R
4
together form a cyclopropyl ring, it being possible for the C—R
5
— and C—R
6
-bonds to be in the E- or Z-position relative to each other;
for controlling phytopathogenic fungal pests.
The invention furthermore relates to novel phenethylacrylamides, to processes for their preparation, and to compositions comprising them.
Various arylacrylamides are disclosed in EP-A 407 217, EP-A 529 736, WO-A 93/01523, JP-A 06/080 616, U.S. Pat. No. 3,657,340, U.S. Pat. No. 3,526,653 and JP-A 63/154 649. Some of them are described as herbicides. However, their fungicidal action is unknown in the prior art.
&agr;-Oximinophenylacetic acid arylamides are described in WO-A 96/17825 and WO-A 96/23763 as fungicides and in JP 02/200 658 as herbicides. In WO-A 96/17825, arylacrylamides are only covered by the general disclosure.
However, the fungicidal action of the [lacuna] described in the abovementioned documents is not satisfactory in many cases. It is therefore an object of the invention to find compounds with an improved action.
It has been found that this object is achieved by the use of the phenylethylacrylamides of the Formula I as fungicides and the novel phenethylacrylamides, and compositions comprising them.
The phenethylacrylamides of the formula I can be prepared by the synthetic routes described in EP-A 407 217, EP-A 529 736, WO-A 93/01523, JP-A 06/080 616, U.S. Pat. No. 3,657,340, U.S. Pat. No. 3,526,653 and JP-A 63/154 649 whose disclosure is herewith incorporated.
The novel phenethylacrylamides in which R
1
and R
2
are identical and are Cl, F and CH
3
can be obtained, for example, starting from &agr;-keto esters of the formula II where R is C
1
-C
4
-alkyl by the routes described hereinbelow:
Compounds in which R
1
and R
2
are chlorine are obtained by reacting &agr;-keto esters of the formula II with triphenylphosphine (PPh
3
) and CCl
4
to give acrylic esters of the formula IIIa. This reaction is usually carried out at temperatures from 10° C. to 120° C., preferably 20° C. to 80° C., in an inert organic solvent [cf. tetrahedron Lett., p. 3003 et seq., 1988].
Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide, dimethyl formamide and dimethyl acetamide, especially preferably acetonitrile and propionitrile. Mixtures of these may also be used.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ CCl
4
and PPh
3
in excess based on II.
Compounds in which R
1
and R
2
are fluorine are obtained by reacting &agr;-keto esters of the formula II with diphenyl-1,1-difluoromethylphosphine of the formula VI where Ph is phenyl, to give acrylic esters of the formula IIIb. This reaction is usually carried out at temperatures from −70° C. to +80° C., preferably 0° C. to 20° C., in an inert organic solvent in the presence of a base [cf. tetrahedron Lett., p. 5571 et seq., 1990].
Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran, especially preferably diethyl ether and tetrahydrofuran. Mixtures of these may also be used.
Suitable bases are, generally, inorganic compounds such as alkali metal hydrides and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, organo metal compounds, in particular alkali metal alkyls such as methyllithium, butyllithium, lithiumdiisopropylamine (LDA) and phenyllithium. Butyllithium and LDA are especially preferred.
In general, the bases are employed in catalytic amounts, and they may also be used in equimolar amounts, in excess or, if appropriate, as solvents.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ VI in an excess based on II.
Alternatively, compounds in which R
1
and R
2
are fluorine, may also be obtained by reacting &agr;-keto esters of the formula II with sodium 2-chloro-2,2-difluoroacetate, of the formula VII, and triphenylphosphine (PPh
3
) to give acrylic esters of the formula IIIb. This reaction is usually carried out at temperatures from 20° C. to 180° C., preferably 60° C. to 180° C., in an inert organic solvent [cf. Org. Synth. Vol. V, p. 949 et seq. (1973)].
Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole, tetrahydrofuran (THF), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and 1,2-diethoxyethane, nitrites such as acetonitrile and propionitrile, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably THF and diethylene glycol dimethyl ether. Mixtures of these may also be used.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ VII in an excess based on II.
Compounds in which R
1
and R
2
are methyl are obtained by reacting &agr;-keto esters of the formula II with iso-propylphosphonium halide of the formula VIII in the sense of a Wittig reaction. Preferred as halides of the formula VIII are iodides and bromides.
In the above reaction scheme, {circle around (P)} in the formula VIII is a phosphoranyl radical, such as, for example, triphenylphosphoranyl.
The Wittig reaction is usually carried out at temperatures from −78° C. to +85° C., preferably −10° C. to +65° C., in an inert organic solvent in the presence of a base [cf. Can. J. Chem. 1971, p. 2143 et seq.].
Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitrites such as acetonitrile and propionitrile, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably diethyl ether and THF. Mixtures of these may also be used.
Suitable bases are, generally, inorganic compounds such as alkali metal hydrides and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, organometal compounds, in particular alkali metal alkyls such as methyllithium, butyllithium, and phenyllithium, alkali metal alkoxides and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium. Sodium hydride and sodium methoxide are especially preferred.
In general, the bases are employed in catalytic amounts, but they may also be used in equimolar amounts, in excess or, if appropriate, as solvent.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advanta

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